CN104157864B - The preparation method of type lithium ion perfluorinated sulfonic resin cladding aluminium lithium alloy material - Google Patents

The preparation method of type lithium ion perfluorinated sulfonic resin cladding aluminium lithium alloy material Download PDF

Info

Publication number
CN104157864B
CN104157864B CN201410333524.2A CN201410333524A CN104157864B CN 104157864 B CN104157864 B CN 104157864B CN 201410333524 A CN201410333524 A CN 201410333524A CN 104157864 B CN104157864 B CN 104157864B
Authority
CN
China
Prior art keywords
lithium
reactor
macropore
carbon
aluminium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201410333524.2A
Other languages
Chinese (zh)
Other versions
CN104157864A (en
Inventor
刘宾虹
李洲鹏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CN201410333524.2A priority Critical patent/CN104157864B/en
Publication of CN104157864A publication Critical patent/CN104157864A/en
Application granted granted Critical
Publication of CN104157864B publication Critical patent/CN104157864B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • H01M4/463—Aluminium based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to technical field of lithium ion, it is desirable to provide the preparation method of type lithium ion perfluorinated sulfonic resin cladding aluminium lithium alloy material.This preparation method includes: prepare the tetrahydrofuran solution of Lithium Aluminium Hydride, prepare macropore material with carbon element, macropore material with carbon element is added the tetrahydrofuran solution of Lithium Aluminium Hydride again, prepares the carbon-supported Lithium Aluminium Hydride composite of macropore, and then obtain the carbon-supported aluminum lithium composite material of macropore；Prepare Li again+Type perfluor sulfoacid resin solution, finally by Li+The carbon-supported Li of macropore prepared by type perfluor sulfoacid resin solution and macropore carbon-supported aluminum lithium composite material+Type perfluorinated sulfonic resin cladding Al-Li Alloy Matrix Composites.Type lithium ion perfluorinated sulfonic resin cladding aluminium lithium alloy material prepared by the present invention has: organic bath is safer in battery applications；Good electrode reaction reversibility；Good chemical stability and heat stability；Cheap and easily prepared；Pollution-free；Antioxidation improves the safety of lithium ion battery.

Description

The preparation method of type lithium ion perfluorinated sulfonic resin cladding aluminium lithium alloy material
Technical field
The present invention is about technical field of lithium ion, particularly to the preparation method that Li ion type perfluoro sulfonate resin is coated with aluminium lithium alloy material.
Background technology
Lithium ion battery has the advantages such as lightweight, capacity big, memory-less effect, thus obtains commonly used.Present many digital equipments all have employed lithium ion battery and make power supply.The energy density of lithium ion battery is significantly high, and its capacity is 1.5～2 times of the Ni-MH battery of same weight, and has very low self-discharge rate, is its wide variety of major reason without advantages such as noxious substances.Nineteen ninety Japan Nagoura et al. is developed into petroleum coke for negative pole, with LiCoO2Lithium ion battery for positive pole: LiC6|LiClO4-PC+EC|LiCoO2.The same year.The lithium ion battery that it is negative pole by release with carbon that the big Battery Company of Moli and Sony two is declared.1991, Sony energy technology company and battery unit developed jointly the lithium ion battery that one is negative pole with polysaccharide alcohol pyrolytic carbon (PFA).
Lithium ion battery negative material has graphite (C6), sulfide: TiS2、NbS2, oxide: WO3、V2O5、SnO2Deng.For graphite cathode material, negative reaction in charge and discharge process: C6+xLi++ xe==LixC6, theoretical capacity is 372mAhg-1(LiC6).When battery is charged, the positive pole of battery having lithium ion to generate, the lithium ion of generation is through electrolyte movement to negative pole.And the graphite as negative pole is layer structure, it has a lot of micropore, and the lithium ion arriving negative pole is just embedded in the micropore of carbon-coating, forms lithium intercalation compound (LixC6), the lithium ion of embedding is more many, and charging capacity is more high.When battery is discharged, the lithium ion being embedded in graphite linings is deviate from, and moves back into again positive pole.The lithium ion returning to positive pole is more many, and discharge capacity is more high.
As the negative material of lithium battery must be possess claimed below: (1) lithium storage capacity is high；(2) lithium embedding in negative material, deintercalation reaction are fast, and namely lithium ion diffusion coefficient in solid phase is big, little in the mobile impedance of electrode-electrolyte interface；(3) lithium ion existence in electrode material is stable；(4) in the charge and discharge cycles of battery, negative material change in volume is little；(5) electron conduction is high；(6) negative material is insoluble in the electrolytic solution.
Metallic aluminium can form up to Li with Li9Al4Alloy, contrast Li4.4Sn(994mAhg-1) there is significantly high theoretical specific capacity (2234mAhg-1), far above traditional graphite cathode material.At Lithium-ion embeding with in the process deviate from, the electric discharge of aluminum honeycomb and charging curve present stable lithium platform embedding, de-respectively in 0.2 and about 0.45V.Therefore, alumina-base material is a kind of very promising lithium ion battery negative material.At present, the encountered subject matter of metallic aluminium negative material is: in charge and discharge cycles process, with Li-Sn alloy phase ratio, the reversible generation of Li-Al alloy and decomposition, along with bigger change in volume, cause that alloy is more easily generated crack and efflorescence, make contact resistance increase, form irreversible capacity loss, even lose reversible lithium storage effect, finally result in electrode failure, therefore simple with aluminum be negative material cycle performance of lithium ion battery very poor.
Even if aluminum particulate can pass through copper or carbon cladding, alleviate the active substance that the efflorescence of aluminum causes in removal lithium embedded process to a certain extent and run off, but its volumetric expansion necessarily causes cracking and the destruction of cladding copper film or carbon film.Therefore, simple copper clad or carbon cladding can not thoroughly solve the metallic aluminium negative pole that the volumetric expansion of aluminum causes in removal lithium embedded process destruction.Must be coated with in the way of aluminium lithium alloy, it is possible to eliminate the volumetric expansion of the aluminum destruction to carrier material in removal lithium embedded process.But, aluminium lithium alloy is quite active, and aluminium lithium alloy particle is coated with by very difficult conventional technological means.
Summary of the invention
Present invention is primarily targeted at and overcome deficiency of the prior art, it is provided that a kind of Li+Type perfluorinated sulfonic resin cladding aluminium lithium alloy, and the preparation method of the lithium ion battery negative material being carrier with macropore carbon.For solving above-mentioned technical problem, the solution of the present invention is:
The preparation method that Li ion type perfluoro sulfonate resin cladding aluminium lithium alloy material is provided, Li ion type perfluoro sulfonate resin cladding aluminium lithium alloy material is for the negative material as lithium battery, and described preparation method specifically includes following step:
(1) in the glove box of argon gas atmosphere, take aluminium powder and lithium sheet is placed in reactor (reactors of 316 stainless steels), remove glove box after sealed reactor, hydrogenation plant is accessed reactor, for passing into hydrogen in reactor and by reactor evacuation；Wherein, the mass ratio of aluminium powder and lithium sheet is 27:7；
(2) by reactor evacuation, vacuum reaches 102After Pascal, the temperature of reactor is risen to 550 DEG C, react 2 hours and generate block lithium-aluminium alloy；After reaction terminates, by reactor cooled to 200 DEG C, and in reactor, pass into 40 atmospheric High Purity Hydrogen (purity: 99.999%) by hydrogenation plant, after reacting 5 hours, cool the temperature to 20 DEG C again, the hydrogen in reactor is discharged, obtains Lithium Aluminium Hydride；
(3) to equipped with, in the reactor (reactors of 316 stainless steels) of Lithium Aluminium Hydride, adding oxolane liquid, stirring and dissolving obtains the tetrahydrofuran solution of Lithium Aluminium Hydride, and making the concentration of Lithium Aluminium Hydride in solution is 2.5wt%～15wt%；
(4) hydrophilic nano CaCO is weighed3And glucose, adding to 100mL deionized water, supersonic vibration (supersonic frequency 40kHz) mixes 30 minutes, makes glucose dissolve and and Nano-meter CaCO33Being uniformly dispersed, heating evaporates the water, and then solidifies 6 hours at 160 DEG C, obtains cured product；Again cured product is warming up to 800 DEG C under nitrogen atmosphere is protected, constant temperature carbonization 2 hours, obtain carbonized product and be cooled to 20 DEG C；Carbonized product is used successively hydrochloric acid and the deionized water wash of 1wt% concentration, then freeze-day with constant temperature, after 4 hours, obtains macropore material with carbon element at 120 DEG C；
Wherein, hydrophilic nano CaCO3It is 1: 1 with the mass ratio of water soluble starch, and hydrophilic nano CaCO3The addition that addition is 10g and glucose be 10g；
(5) take the macropore material with carbon element prepared in step (4) and add the tetrahydrofuran solution of the Lithium Aluminium Hydride obtained in step (3), after ultrasonic (supersonic frequency 40kHz) mixes 30min, evaporate oxolane, namely obtain the carbon-supported Lithium Aluminium Hydride composite of macropore；
(6) the carbon-supported Lithium Aluminium Hydride composite of macropore prepared in step (5) is placed in reactor (reactors of 316 stainless steels), at 400 DEG C, evacuation is after 4 hours, namely obtain the carbon-supported aluminum lithium composite material of macropore, and carbon-supported for macropore aluminum lithium composite material is cooled to 20 DEG C；
(7) take perfluorinated sulfonic resin 10g (originating from E.I.Du Pont Company) and be placed in 100mLLiOH aqueous solution, after stirring 2 hours at 80 DEG C, be filtrated to get product；After taking out product and cleaning with deionized water, carry out vacuum drying, obtain Li+Type perfluorinated sulfonic resin；
Take the 10g Li prepared again+Type perfluorinated sulfonic resin is dissolved in 200mLN-methyl pyrrolidone (NMP), namely obtains Li+Type perfluor sulfoacid resin solution；
(8) in the glove box of argon gas atmosphere, the Li prepared in step (7) is taken+Type perfluor sulfoacid resin solution is added in the carbon-supported aluminum lithium composite material of macropore prepared in step (6), is evaporated, namely obtains the carbon-supported Li of macropore after stirring at 150 DEG C+Type perfluorinated sulfonic resin cladding Al-Li Alloy Matrix Composites；
Wherein, Li+The addition of type perfluor sulfoacid resin solution is 50～200mL, and the addition of the carbon-supported aluminum lithium composite material of macropore is 1g.
As further improvement, in the glove box of described argon gas atmosphere, water content and oxygen content are respectively less than 1ppm.
As further improvement, the perfluorinated sulfonic resin in described step (7) adopts thin film or pulverous perfluorinated sulfonic resin.
As further improvement, the LiOH aqueous solution in described step (7) is mass concentration is the LiOH aqueous solution of 10wt%.
As further improvement, described hydrophilic nano CaCO3Particle diameter be 15～40nm.
As further improvement, the hydrogenation plant in described step (1), including air relief valve, high-purity High Pressure Hydrogen bottle, hydrogen storehouse, Pressure gauge, unidirectional stop valve, vacuum pump, pipeline docking adapter, vacuum meter；
High-purity High Pressure Hydrogen bottle (1-1), air relief valve (1-6), hydrogen storehouse (1-3), unidirectional stop valve (1-10) are sequentially connected with, and hydrogen storehouse (1-3) is connected to Pressure gauge (1-11)；Unidirectional stop valve (1-9) it is connected between hydrogen storehouse (1-3) and unidirectional stop valve (1-10), unidirectional stop valve (1-9) is connected with vacuum pump (1-4), is also associated with vacuum meter (1-12) between unidirectional stop valve (1-9) and vacuum pump (1-4)；Hydrogen storehouse (1-3) is also associated with unidirectional stop valve (1-8), and unidirectional stop valve (1-8) is connected with pipeline docking adapter (1-5)；
Reactor is connected to unidirectional stop valve (1-7), and is connected with the pipeline docking adapter (1-5) in hydrogenation plant by unidirectional stop valve (1-7).
As further improvement, the intensification of described reactor is heated by being arranged in electric furnace by reactor, utilizes the heating of electric furnace to realize.
The operation principle of the present invention:
In step (2), aluminum and lithium generate block lithium-aluminium alloy after reacting 2 hours at 550 DEG C.Owing to aluminium lithium alloy is extremely active, there is spontaneous combustion blast in atmosphere, therefore, it is difficult to directly use.Aluminium lithium alloy is cooled to 200 DEG C and passes into and generate Lithium Aluminium Hydride after 40 atmospheric High Purity Hydrogen.Lithium Aluminium Hydride is stable in dry air, can be dissolved in oxolane.
In step (5), in being evaporated process, Lithium Aluminium Hydride in macropore material with carbon element endoporus crystallization and be filled in macropore carbon endoporus.
In step (6), at 400 DEG C, during evacuation, Lithium Aluminium Hydride puts hydrogen by stage:
3LiAlH4→Li3AlH6+2Al+3H2
2Li3AlH6→6LiH+2Al+3H2
2LiH+2Al→2LiAl+H2
Putting hydrogen after 4 hours to terminate, particle size reduces, and leaves a void between lithium-aluminium alloy particle and macropore carbon inwall, the volumetric expansion that in available buffer lithium cell charging process, the embedding lithium of lithium-aluminium alloy particle produces, it is to avoid the destruction to macropore material with carbon element.
In step (8), it is evaporated process at 150 DEG C and makes Li+Type perfluorinated sulfonic resin solidifies at aluminium lithium alloy particle surface, forms clad, makes aluminium lithium alloy and air exclusion, aluminium lithium alloy also can be suppressed to react with electrolyte, but do not affect the conduction of lithium ion during aluminium lithium alloy particle removal lithium embedded.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention utilizes aluminum to have the characteristic of high storage lithium specific capacity, forms the lithium ion battery negative material of a kind of high power capacity；Lithium Aluminium Hydride tetrahydrofuran solution is conducive to being filled to equably by Lithium Aluminium Hydride in the mesoporous of macropore material with carbon element and macropore, advantageously forms the carbon-supported Li of macropore that aluminium lithium alloy is evenly distributed+Type perfluorinated sulfonic resin cladding Al-Li Alloy Matrix Composites；Li+Type perfluorinated sulfonic resin clad makes aluminium lithium alloy and air exclusion, is greatly enhanced the safety of this negative material.
The carbon-supported Li of macropore prepared by the present invention+Type perfluorinated sulfonic resin cladding Al-Li Alloy Matrix Composites, has: (1) charging/discharging voltage platform smoothly makes organic bath safer in battery applications；(2) good electrode reaction reversibility；(3) good chemical stability and heat stability；(4) cheap and easily prepared；(5) pollution-free；(6) antioxidation improves the safety of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the device schematic diagram preparing Lithium Aluminium Hydride in embodiment 1.
Fig. 2 is the lithium ion battery charging and discharging curve schematic diagram of embodiment nine preparation.
Accompanying drawing in figure is labeled as: the high-purity High Pressure Hydrogen bottle of 1-1；1-2 reactor；1-3 hydrogen storehouse；1-4 vacuum pump；1-5 pipeline docking adapter；1-6 air relief valve；1-7 unidirectional stop valve；1-8 unidirectional stop valve；1-9 unidirectional stop valve；1-10 unidirectional stop valve；1-11 Pressure gauge；1-12 vacuum meter；1-13 electric furnace；2-1 charging curve；2-2 discharge curve.
Detailed description of the invention
Below in conjunction with accompanying drawing and detailed description of the invention, the present invention is described in further detail:
The preparation method of Li ion type perfluoro sulfonate resin cladding aluminium lithium alloy material, Li ion type perfluoro sulfonate resin cladding aluminium lithium alloy material is for the negative material as lithium battery, and described preparation method specifically includes following step:
(1) it is respectively less than in the glove box of argon gas atmosphere of 1ppm at water content and oxygen content, takes aluminium powder and lithium sheet is placed in the reactor 1-2 of 316 stainless steels, remove glove box after sealed reactor 1-2, access hydrogenation plant；Wherein, the mass ratio of aluminium powder and lithium sheet is 27:7；
(2) by reactor 1-2 evacuation, vacuum reaches 102After Pascal, the temperature of reactor 1-2 is risen to 550 DEG C, react 2 hours and generate block lithium-aluminium alloy；Reactor 1-2 is cooled to 200 DEG C, and passes into 40 atmospheric High Purity Hydrogen (purity: 99.999%) in reactor 1-2, react 5 hours after terminating by reaction；Temperature is down to 20 DEG C, is discharged by the hydrogen in reactor 1-2, obtains Lithium Aluminium Hydride；
(3) adding oxolane liquid in the reactor 1-2 of 316 stainless steels containing Lithium Aluminium Hydride, stirring and dissolving obtains the tetrahydrofuran solution of Lithium Aluminium Hydride；Wherein the concentration of Lithium Aluminium Hydride is determined by the addition of oxolane；The concentration of Lithium Aluminium Hydride is 2.5wt%～15wt%；
(4) Nano-meter CaCO3 that commercially available particle diameter be 15～40nm is weighed at 1: 1 in mass ratio3(10g) with glucose (10g), adding to 100mL deionized water, supersonic vibration (supersonic frequency 40kHz) mixes 30 minutes makes glucose dissolve and and Nano-meter CaCO33It is uniformly dispersed；Heating evaporates the water, and then solidifies 6 hours at 160 DEG C；Cured product is warming up to 800 DEG C under nitrogen atmosphere protection, constant temperature carbonization 2 hours；It is cooled to 20 DEG C.Product uses hydrochloric acid and the deionized water wash of 1wt% concentration successively, then freeze-day with constant temperature, after 4 hours, obtains macropore material with carbon element at 120 DEG C.
(5) take the macropore material with carbon element prepared in step (4) and add the Lithium Aluminium Hydride tetrahydrofuran solution obtained in step (3), after ultrasonic (supersonic frequency 40kHz) mixes 30min, evaporate oxolane, obtain the carbon-supported Lithium Aluminium Hydride composite of macropore；
(6) being placed in the reactor 1-2 of 316 stainless steels by the carbon-supported Lithium Aluminium Hydride composite of macropore prepared in step (5), at 400 DEG C, evacuation is after 4 hours, namely obtains the carbon-supported aluminum lithium composite material of macropore, is cooled to 20 DEG C；
(7) take thin film or pulverous perfluorinated sulfonic resin 10g (originating from E.I.Du Pont Company) is placed in the LiOH aqueous solution of 100mL10wt%, after stirring 2 hours at 80 DEG C, be filtrated to get product；After taking out product and cleaning with deionized water, carry out vacuum drying, obtain Li+Type perfluorinated sulfonic resin；
Again by prepared Li+Type perfluorinated sulfonic resin is dissolved in 200mLN-methyl pyrrolidone (NMP), namely obtains Li+Type perfluor sulfoacid resin solution；
(8) it is respectively less than in the glove box of argon gas atmosphere of 1ppm at water content and oxygen content, takes the Li prepared in step (7)+Type perfluor sulfoacid resin solution is added in the carbon-supported aluminum lithium composite material of macropore prepared in step (6), is evaporated, namely obtains the carbon-supported Li of macropore after stirring+Type perfluorinated sulfonic resin cladding Al-Li Alloy Matrix Composites；
Wherein, Li+The addition of type perfluor sulfoacid resin solution is 50～200mL, and the addition of the carbon-supported aluminum lithium composite material of macropore is 1g.
Hydrogenation plant therein includes air relief valve, high-purity High Pressure Hydrogen bottle, hydrogen storehouse, Pressure gauge, unidirectional stop valve, vacuum pump, pipeline docking adapter, vacuum meter.High-purity High Pressure Hydrogen bottle 1-1, air relief valve 1-6, hydrogen storehouse 1-3, unidirectional stop valve 1-10 are sequentially connected with, and hydrogen storehouse 1-3 is connected to Pressure gauge 1-11；Being connected to unidirectional stop valve 1-9 between hydrogen storehouse 1-3 and unidirectional stop valve 1-10, unidirectional stop valve 1-9 is connected with vacuum pump 1-4, is also associated with vacuum meter 1-12 between unidirectional stop valve 1-9 and vacuum pump 1-4；Hydrogen storehouse 1-3 is also associated with unidirectional stop valve 1-8, unidirectional stop valve 1-8 and is connected to unidirectional stop valve 1-7 with pipeline docking adapter 1-5 coupled reaction device 1-2, and is connected with the pipeline docking adapter 1-5 in hydrogenation plant by unidirectional stop valve 1-7.
It addition, the intensification of reactor 1-2 is heated by being arranged in electric furnace 1-13, the heating of electric furnace 1-13 is utilized to realize
The following examples can make the professional and technical personnel of this specialty more fully understand the present invention, but does not limit the present invention in any way.
Prepared by embodiment 1 Lithium Aluminium Hydride
In the glove box of argon atmospher protection (water content and oxygen content are respectively less than 1ppm); take aluminium powder 27g; lithium sheet 7g is placed in the reactor of 316 stainless steels; glove box is removed after sealed reactor; hydrogenation plant is accessed by pipeline docking adapter 1-5; as it is shown in figure 1, all valves of hydrogenation plant are initial is in closed mode.Open stop valve 1-7,1-8,1-9, be evacuated to vacuum meter 1-12 and show 102Stop valve 1-9 is closed after Pascal.Electric furnace 1-13 is warming up to 550 DEG C, when temperature of reactor rise to 550 DEG C reaction 2 little time after, be cooled to 200 DEG C；Opening air relief valve 1-6 makes the High Purity Hydrogen (purity: 99.999%) in high-purity High Pressure Hydrogen bottle 1-1 be filled with hydrogen storehouse 1-3, makes the pressure of hydrogen in reactor 1-3 maintain 40 atmospheric pressure, and hydrogen pressure is shown by Pressure gauge 1-11；Open stop valve 1-7 and 1-8, make High Purity Hydrogen enter reactor；After reacting 5 hours, close air relief valve 1-6, open stop valve 1-10 and carry out putting hydrogen, after discharging the hydrogen in reactor, close stop valve 1-10, furnace temperature is down to 20 DEG C and obtains Lithium Aluminium Hydride.
Prepared by embodiment 2 Lithium Aluminium Hydride tetrahydrofuran solution
In the glove box of argon atmospher protection (water content and oxygen content are respectively less than 1ppm); take aluminium powder 2.7g; lithium sheet 0.7g is placed in the reactor of 316 stainless steels; glove box is removed after sealed reactor; hydrogenation plant is accessed by pipeline docking adapter 1-5; as it is shown in figure 1, all valves of hydrogenation plant are initial is in closed mode.Open stop valve 1-7,1-8,1-9, be evacuated to vacuum meter 1-12 and show 102Stop valve 1-9 is closed after Pascal.Electric furnace 1-13 is warming up to 550 DEG C, when temperature of reactor rise to 550 DEG C reaction 2 little time after, be cooled to 200 DEG C；Opening air relief valve 1-6 makes the High Purity Hydrogen (purity: 99.999%) in high-purity High Pressure Hydrogen bottle 1-1 be filled with hydrogen storehouse 1-3, makes the pressure of hydrogen in reactor 1-3 maintain 40 atmospheric pressure, and hydrogen pressure is shown by Pressure gauge 1-11；Open stop valve 1-7 and 1-8, make High Purity Hydrogen enter reactor；After reacting 5 hours, close air relief valve 1-6, open stop valve 1-10 to carry out putting hydrogen, after discharging the hydrogen in reactor, close stop valve 1-10, furnace temperature is down to 20 DEG C, open stop valve 1-9 and pump remaining hydrogen in reactor, close stop valve 1-9, open reactor, adding 75mL oxolane, stirring and dissolving obtains the tetrahydrofuran solution containing 5.3wt% Lithium Aluminium Hydride.
After opening reactor, if the 26.5mL oxolane only added, the tetrahydrofuran solution that stirring and dissolving will obtain containing 15wt% Lithium Aluminium Hydride；But the oxolane added reaches 159mL, the tetrahydrofuran solution that stirring and dissolving will obtain containing 2.5wt% Lithium Aluminium Hydride.
Prepared by embodiment 3 macropore material with carbon element
Particle diameter is the Nano-meter CaCO3 of 15～40nm310g and glucose 10g, adds to 100mL deionized water, and supersonic vibration (supersonic frequency 40kHz) mixes 30 minutes makes glucose dissolve and and Nano-meter CaCO33It is uniformly dispersed；Heating evaporates the water, and then solidifies 6 hours at 160 DEG C；Cured product is warming up to 800 DEG C under nitrogen atmosphere protection, constant temperature carbonization 2 hours；It is cooled to 20 DEG C.Product uses hydrochloric acid and the deionized water wash of 1wt% concentration successively, then freeze-day with constant temperature, after 4 hours, obtains macropore material with carbon element at 120 DEG C.
Prepared by the carbon-supported Lithium Aluminium Hydride composite of embodiment 4 macropore
In the glove box of argon atmospher protection (water content and oxygen content are respectively less than 1ppm); take aluminium powder 27g; lithium sheet 7g is placed in the reactor of 316 stainless steels; glove box is removed after sealed reactor; hydrogenation plant is accessed by pipeline docking adapter 1-5; as it is shown in figure 1, all valves of hydrogenation plant are initial is in closed mode.Open stop valve 1-7,1-8,1-9, be evacuated to vacuum meter 1-12 and show 102Stop valve 1-9 is closed after Pascal.Electric furnace 1-13 is warming up to 550 DEG C, when temperature of reactor rise to 550 DEG C reaction 2 little time after, be cooled to 200 DEG C；Opening air relief valve 1-6 makes the High Purity Hydrogen (purity: 99.999%) in high-purity High Pressure Hydrogen bottle 1-1 be filled with hydrogen storehouse 1-3, makes the pressure of hydrogen in reactor 1-3 maintain 40 atmospheric pressure, and hydrogen pressure is shown by Pressure gauge 1-11；Open stop valve 1-7 and 1-8, make High Purity Hydrogen enter reactor；After reacting 5 hours, close air relief valve 1-6, open stop valve 1-10 to carry out putting hydrogen, after discharging the hydrogen in reactor, close stop valve 1-10, furnace temperature is down to 20 DEG C, open stop valve 1-9 and pump remaining hydrogen in reactor, close stop valve 1-9, open reactor, adding 375mL oxolane, stirring and dissolving obtains the tetrahydrofuran solution containing 10.1wt% Lithium Aluminium Hydride.
Macropore carbon 10g in Example three adds Lithium Aluminium Hydride tetrahydrofuran solution 100mL derived above, ultrasonic (supersonic frequency 40kHz) evaporates oxolane after mixing 30min, obtains the carbon-supported Lithium Aluminium Hydride composite of the macropore containing 47.6wt% Lithium Aluminium Hydride content.
Prepared by the carbon-supported Al-Li Alloy Matrix Composites of embodiment 5 macropore
The carbon-supported Lithium Aluminium Hydride composite of macropore obtained in Example four, is placed in the reactor of 316 stainless steels, and at 400 DEG C, evacuation is after 4 hours, is cooled to 20 DEG C and obtains the carbon-supported Al-Li Alloy Matrix Composites of macropore.
Embodiment 6Li+Prepared by type perfluor sulfoacid resin solution
By city buy to resell perfluorinated sulfonic resin thin film 10g (originating from E.I.Du Pont Company) be placed in 100mLLiOH aqueous solution (10wt%), 80 DEG C stirring 2 hours after filter, taking-up deionized water clean after carry out vacuum drying, obtain Li+Type perfluorinated sulfonic resin；It is dissolved in 200mLN-methyl pyrrolidone (NMP), obtains the Li that concentration is 4.76wt%+Type perfluor sulfoacid resin solution.
The carbon-supported Li of embodiment 7 macropore+Type perfluorinated sulfonic resin cladding Al-Li Alloy Matrix Composites
In the glove box of argon atmospher protection (water content and oxygen content are respectively less than 1ppm), carbon-supported for the macropore obtained by embodiment four, five aluminum lithium composite material (1g) is added into the 50mLLi that embodiment six obtains+In type perfluor sulfoacid resin solution, it is evaporated after stirring, obtains the carbon-supported Li of macropore+Type perfluorinated sulfonic resin cladding Al-Li Alloy Matrix Composites.
Embodiment 8 is with the carbon-supported Li of macropore+Prepared by the negative pole of type perfluorinated sulfonic resin cladding aluminium lithium alloy
In the glove box of argon atmospher protection (water content and oxygen content are respectively less than 1ppm), carbon-supported for the macropore obtained by embodiment four, five aluminum lithium composite material (1g) is added into the 100mLLi that embodiment six obtains+In type perfluor sulfoacid resin solution, stir and be evaporated at latter 150 DEG C, obtain the carbon-supported Li of macropore+Type perfluorinated sulfonic resin cladding Al-Li Alloy Matrix Composites.
By above-mentioned negative material: Li+Type perfluorinated sulfonic resin: acetylene black is 80: 10: 10 in mass ratio, mechanical mixture 30 minutes, the appropriate NMP that adds is modulated into paste, is coated on copper film, dries in the shade；At 100Kgcm-2Pressure make type, obtain negative pole.
Embodiment 9 is with the carbon-supported Li of macropore+Type perfluorinated sulfonic resin cladding aluminium lithium alloy is the lithium battery of negative material
In the glove box of argon atmospher protection (water content and oxygen content are respectively less than 1ppm), carbon-supported for the macropore obtained by embodiment four, five aluminum lithium composite material (1g) is added into the 200mLLi that embodiment six obtains+In type perfluor sulfoacid resin solution, stir and be evaporated at latter 150 DEG C, obtain the carbon-supported Li of macropore+Type perfluorinated sulfonic resin cladding Al-Li Alloy Matrix Composites.
By above-mentioned negative material: Li+Type perfluorinated sulfonic resin: acetylene black is 80: 10: 10 in mass ratio, mechanical mixture 30 minutes, the appropriate NMP that adds is modulated into paste, is coated on copper film, and the final vacuum that dries in the shade dries；At 100Kgcm-2Pressure make type, obtain negative pole.
By anode material for lithium-ion batteries nano-TiO2∶Li+Type perfluorinated sulfonic resin: acetylene black is 80: 10: 10 in mass ratio, mechanical mixture 30 minutes, the appropriate NMP that adds is modulated into paste, is modulated into paste, is coated on aluminum film, and the final vacuum that dries in the shade dries；At 100Kgcm-2Pressure make type, obtain TiO2Positive pole.
With microporous polypropylene membrane for barrier film, the electrode material side of above-mentioned positive pole and negative pole forms sandwich structure, built-in electrolyte with barrier film in opposite directions；Electrolyte is with LiPF6For solute, ethylene carbonate is solvent, containing 151.9 grams of lithium hexafluoro phosphates in one liter of electrolyte.Fig. 2 is the charging and discharging curve of assembled battery.Abscissa unit is the electricity that every gram of aluminum discharges.Charge-discharge magnification: 0.2C, temperature: 25 DEG C.
Finally it should be noted that listed above is only specific embodiments of the invention.It is clear that the invention is not restricted to above example, it is also possible to there is many variations.All deformation that those of ordinary skill in the art can directly derive from present disclosure or associate, are all considered as protection scope of the present invention.

Claims (7)

  1. The preparation method of 1.Li ion type perfluoro sulfonate resin cladding aluminium lithium alloy material, Li ion type perfluoro sulfonate resin cladding aluminium lithium alloy material is for the negative material as lithium battery, it is characterised in that described preparation method specifically includes following step:
    (1) in the glove box of argon gas atmosphere, take aluminium powder and lithium sheet is placed in reactor, remove glove box after sealed reactor, hydrogenation plant is accessed reactor, for passing into hydrogen in reactor and by reactor evacuation；Wherein, the mass ratio of aluminium powder and lithium sheet is 27:7；
    (2) by reactor evacuation, vacuum reaches 102After Pascal, the temperature of reactor is risen to 550 DEG C, react 2 hours and generate block lithium-aluminium alloy；After reaction terminates, by reactor cooled to 200 DEG C, and in reactor, pass into 40 atmospheric High Purity Hydrogen by hydrogenation plant, after reacting 5 hours, then cool the temperature to 20 DEG C, the hydrogen in reactor is discharged, obtains Lithium Aluminium Hydride；
    (3) to equipped with, in the reactor of Lithium Aluminium Hydride, adding oxolane liquid, stirring and dissolving obtains the tetrahydrofuran solution of Lithium Aluminium Hydride, and making the concentration of Lithium Aluminium Hydride in solution is 2.5wt%～15wt%；
    (4) hydrophilic nano CaCO is weighed3And glucose, adding to 100mL deionized water, supersonic vibration mixes 30 minutes, makes glucose dissolve and and Nano-meter CaCO33Being uniformly dispersed, heating evaporates the water, and then solidifies 6 hours at 160 DEG C, obtains cured product；Again cured product is warming up to 800 DEG C under nitrogen atmosphere is protected, constant temperature carbonization 2 hours, obtain carbonized product and be cooled to 20 DEG C；Carbonized product is used successively hydrochloric acid and the deionized water wash of 1wt% concentration, then freeze-day with constant temperature, after 4 hours, obtains macropore material with carbon element at 120 DEG C；
    Wherein, hydrophilic nano CaCO3Be 1: 1 with the mass ratio of glucose, i.e. hydrophilic nano CaCO3With the addition of glucose all respectively 10g；
    (5) take the macropore material with carbon element prepared in step (4) and add the tetrahydrofuran solution of the Lithium Aluminium Hydride obtained in step (3), after ultrasonic mixing 30min, evaporate oxolane, namely obtain the carbon-supported Lithium Aluminium Hydride composite of macropore；
    (6) the carbon-supported Lithium Aluminium Hydride composite of macropore prepared in step (5) is placed in reactor, at 400 DEG C, evacuation is after 4 hours, namely obtain the carbon-supported aluminum lithium composite material of macropore, and carbon-supported for macropore aluminum lithium composite material is cooled to 20 DEG C；
    (7) take perfluorinated sulfonic resin 10g and be placed in 100mLLiOH aqueous solution, after stirring 2 hours at 80 DEG C, be filtrated to get product；After taking out product and cleaning with deionized water, carry out vacuum drying, obtain Li+Type perfluorinated sulfonic resin；
    Take the 10g Li prepared again+Type perfluorinated sulfonic resin is dissolved in 200mLN-methyl pyrrolidone, namely obtains Li+Type perfluor sulfoacid resin solution；
    (8) in the glove box of argon gas atmosphere, the Li prepared in step (7) is taken+Type perfluor sulfoacid resin solution is added in the carbon-supported aluminum lithium composite material of macropore prepared in step (6), is evaporated, namely obtains the carbon-supported Li of macropore after stirring at 150 DEG C+Type perfluorinated sulfonic resin cladding Al-Li Alloy Matrix Composites；
    Wherein, Li+The addition of type perfluor sulfoacid resin solution is 50～200mL, and the addition of the carbon-supported aluminum lithium composite material of macropore is 1g.
  2. 2. the preparation method of Li ion type perfluoro sulfonate resin according to claim 1 cladding aluminium lithium alloy material, it is characterised in that in the glove box of described argon gas atmosphere, water content and oxygen content are respectively less than 1ppm.
  3. 3. the preparation method of Li ion type perfluoro sulfonate resin according to claim 1 cladding aluminium lithium alloy material, it is characterised in that the perfluorinated sulfonic resin in described step (7) adopts thin film or pulverous perfluorinated sulfonic resin.
  4. 4. the preparation method of Li ion type perfluoro sulfonate resin according to claim 1 cladding aluminium lithium alloy material, it is characterised in that the LiOH aqueous solution in described step (7) is mass concentration is the LiOH aqueous solution of 10wt%.
  5. 5. the preparation method of Li ion type perfluoro sulfonate resin according to claim 1 cladding aluminium lithium alloy material, it is characterised in that described hydrophilic nano CaCO3Particle diameter be 15～40nm.
  6. 6. the preparation method of Li ion type perfluoro sulfonate resin according to claim 1 cladding aluminium lithium alloy material, it is characterized in that, hydrogenation plant in described step (1), including air relief valve, high-purity High Pressure Hydrogen bottle, hydrogen storehouse, Pressure gauge, unidirectional stop valve, vacuum pump, pipeline docking adapter, vacuum meter；
    High-purity High Pressure Hydrogen bottle (1-1), air relief valve (1-6), hydrogen storehouse (1-3), unidirectional stop valve (1-10) are sequentially connected with, and hydrogen storehouse (1-3) is connected to Pressure gauge (1-11)；Unidirectional stop valve (1-9) it is connected between hydrogen storehouse (1-3) and unidirectional stop valve (1-10), unidirectional stop valve (1-9) is connected with vacuum pump (1-4), is also associated with vacuum meter (1-12) between unidirectional stop valve (1-9) and vacuum pump (1-4)；Hydrogen storehouse (1-3) is also associated with unidirectional stop valve (1-8), and unidirectional stop valve (1-8) is connected with pipeline docking adapter (1-5)；
    Reactor is connected to unidirectional stop valve (1-7), and is connected with the pipeline docking adapter (1-5) in hydrogenation plant by unidirectional stop valve (1-7).
  7. 7. the preparation method of Li ion type perfluoro sulfonate resin according to claim 1 cladding aluminium lithium alloy material, it is characterised in that the intensification of described reactor is heated by being arranged in electric furnace by reactor, utilizes the heating of electric furnace to realize.
CN201410333524.2A 2014-07-14 2014-07-14 The preparation method of type lithium ion perfluorinated sulfonic resin cladding aluminium lithium alloy material Expired - Fee Related CN104157864B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410333524.2A CN104157864B (en) 2014-07-14 2014-07-14 The preparation method of type lithium ion perfluorinated sulfonic resin cladding aluminium lithium alloy material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410333524.2A CN104157864B (en) 2014-07-14 2014-07-14 The preparation method of type lithium ion perfluorinated sulfonic resin cladding aluminium lithium alloy material

Publications (2)

Publication Number Publication Date
CN104157864A CN104157864A (en) 2014-11-19
CN104157864B true CN104157864B (en) 2016-07-06

Family

ID=51883317

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410333524.2A Expired - Fee Related CN104157864B (en) 2014-07-14 2014-07-14 The preparation method of type lithium ion perfluorinated sulfonic resin cladding aluminium lithium alloy material

Country Status (1)

Country Link
CN (1) CN104157864B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104592541B (en) * 2015-01-20 2017-10-27 浙江大学 Micropore polybenzimidazole membrane and modified polyphenyl and imidazoles are the lithium-sulfur cell of barrier film
CN105514374B (en) * 2015-12-11 2019-01-01 武汉理工大学 A kind of graphitized carbon cladding manganese OXYFLUORIDE MATERIALS and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20011034A1 (en) * 2001-05-18 2002-11-18 Ausimont Spa PROCESS FOR THE PREPARATION OF FLUOROPOLOSSOALKYLENS WITH A TERMINAL -CH 2OH AND THE OTHER TERMINAL CONTAINING CHLORINE
CN1242502C (en) * 2003-03-28 2006-02-15 中国科学院上海微系统与信息技术研究所 Silicon aluminium alloy/carbon composite material used for lithium ion battery negative electrode and its preparation method
CN101759858B (en) * 2008-11-14 2012-07-18 山东华夏神舟新材料有限公司 Preparation method of high-boiling point salt type perfluor sulfoacid resin solution

Also Published As

Publication number Publication date
CN104157864A (en) 2014-11-19

Similar Documents

Publication Publication Date Title
CN109728259B (en) Silicon-based composite anode material, preparation method thereof and energy storage device
CN106876689B (en) Nitrogen-doped graphene-silicon composite negative electrode material, preparation method thereof and lithium ion battery
CN110668509B (en) Selenium-coated high-nickel ternary layered positive electrode material and preparation method thereof
CN112768662A (en) High-nickel ternary layered cathode material coated by low-temperature vapor deposition and preparation method thereof
CN108598444B (en) Vanadium trioxide/graphene composite negative electrode material of lithium ion battery and preparation method
CN107978738B (en) Manganese sodium pyrophosphate/carbon composite cathode material and preparation and application thereof
CN104009212B (en) A kind of preparation method of graphene-based nano silicon complex electrode material
CN111640927B (en) Graphene-bridged polythiophene-coated germanium nanoparticle composite material and preparation method and application thereof
CN104852020A (en) Lithium ion battery silicon oxide composite negative electrode material and preparation method thereof
WO2022252111A1 (en) Lithium manganese oxide positive electrode active material, positive electrode plate containing same, secondary battery, battery module, battery pack and electrical device
CN105047861A (en) Sulfur-carbon composite material and preparation method thereof
CN108281627B (en) Germanium-carbon composite negative electrode material for lithium ion battery and preparation method thereof
CN116826001A (en) Electrolyte doped sulfur/carbon composite positive electrode material and preparation method thereof
CN113889594A (en) Preparation method of boron-doped lithium lanthanum zirconate-coated graphite composite material
CN105047870A (en) Nitrogen-doped carbon-coated silicon composite material and preparation method thereof
CN113675382B (en) Sn/MoS 2 @ C composite material and preparation method and application thereof
CN114039051A (en) MXene/SnO with three-dimensional structure2/C negative electrode composite material and preparation method thereof
CN104157864B (en) The preparation method of type lithium ion perfluorinated sulfonic resin cladding aluminium lithium alloy material
CN111162269B (en) Negative electrode active material for battery and preparation method thereof
CN113072045A (en) Negative electrode active material, preparation method thereof, negative electrode material, negative electrode and potassium ion battery
CN109461917B (en) Preparation method of lanthanum zirconate in-situ coated high-nickel ternary cathode material
CN112421049A (en) Method for preparing lithium battery silicon-carbon negative electrode material through ball milling and silicon-carbon negative electrode material
CN111525115A (en) Etched nano-silicon double-layer carbon-coated lithium ion battery negative electrode material, negative electrode plate and preparation method of negative electrode plate
CN108461741B (en) LiAlO2/C modified ternary composite material and preparation method and application thereof
CN108172813B (en) Composite cathode material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160706

Termination date: 20190714

CF01 Termination of patent right due to non-payment of annual fee